TY - JOUR
T1 - Dual-Functional Tamm-Dancoff Approximation
T2 - A Convenient Density Functional Method that Correctly Describes S1/S0 Conical Intersections
AU - Shu, Yinan
AU - Parker, Kelsey A.
AU - Truhlar, Donald G.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/5/18
Y1 - 2017/5/18
N2 - Time-dependent Kohn-Sham density functional theory has been used successfully to compute vertical excitation energies, especially for large molecular systems. However, the lack of double excitation character in the excited amplitudes produced by linear response in the adiabatic approximation holds it back from broader applications in photochemistry; for example, it shows (3N - 7)-dimensional conical intersection seams (where N is the number of atoms) between ground and excited states, although the correct dimensionality is 3N - 8. In this letter, we present a new, conceptually simple, easy-to-implement, and easy-to-use way to employ time-dependent Kohn-Sham density functional theory that has global accuracy comparable with the conventional single-functional version and that recovers the double cone topology of the potential energy surfaces at S1/S0 conical intersection seams. The new method is called the dual-functional Tamm-Dancoff approximation (DF-TDA).
AB - Time-dependent Kohn-Sham density functional theory has been used successfully to compute vertical excitation energies, especially for large molecular systems. However, the lack of double excitation character in the excited amplitudes produced by linear response in the adiabatic approximation holds it back from broader applications in photochemistry; for example, it shows (3N - 7)-dimensional conical intersection seams (where N is the number of atoms) between ground and excited states, although the correct dimensionality is 3N - 8. In this letter, we present a new, conceptually simple, easy-to-implement, and easy-to-use way to employ time-dependent Kohn-Sham density functional theory that has global accuracy comparable with the conventional single-functional version and that recovers the double cone topology of the potential energy surfaces at S1/S0 conical intersection seams. The new method is called the dual-functional Tamm-Dancoff approximation (DF-TDA).
UR - http://www.scopus.com/inward/record.url?scp=85019363580&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85019363580&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.7b00594
DO - 10.1021/acs.jpclett.7b00594
M3 - Article
C2 - 28418680
AN - SCOPUS:85019363580
SN - 1948-7185
VL - 8
SP - 2107
EP - 2112
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 10
ER -